As-synthesized CTA-MCM-41 silica possesses basic siloxy (equivalent to SiO-) catalytic sites, enabling it to be used in reactions such as transesterification and Knoevenagel condensation, Its application in basic catalysis has shown promising results, but attempts to reuse it in more than one cycle has revealed rapid loss of activity due to the removal of cetyltrimethylammonium (CTA) cations from the interior of the channels. The present work describes the encapsulation of nanoparticulate methacrylic polymers during the conventional synthesis of MCM-41, resulting in hybrid silicas containing polymers in the interior of the inorganic and organic matrix. Aqueous dispersions containing surfactant and monomers were characterized by small-angle X-ray scattering (SAXS), which confirmed the expansion of the micelles due to the presence of the encapsulated monomers. Transmission electron microscopy (TEM) was used to observe the formation of polymer nanoparticles stabilized by the surfactant (cetyltrimethy lammonium bromide). Infrared absorption spectroscopy and chemical analysis showed that these particles were present in the material after the synthesis. Analysis of the silicas using SAXS and nitrogen physisorption showed the expansion of the channels of the CTA-MCM-41 and the formation of two mesopore systems in the silica. Catalytic evaluation demonstrated that the silicas synthesized in the presence of the emulsified polymers possessed better catalytic stability when low monomer contents and monomers with larger alkyl chains were used. The encapsulation of nanoparticles of methacrylic polymer in the interior of the CTA-MCM-41 channels helped to avoid leaching of the CTA cations during the reaction. (C) 2016 Elsevier B.V. All rights reserved.